Conventional Electron Paramagnetic Resonance Research Articles

Coherent Addressing of Single Molecular Electron Spin Qubits

AbstractWith rational designability, versatile tunability, and quantum coherence, molecular electron spin qubits could offer new opportunities for quantum information science, enabling simplified implementation of quantum algorithms and chemical‐specific quantum sensing. The development of these transformative technologies relies on coherent addressing of single molecular electron spin qubits with high initialization, manipulation, and readout fidelities. This is unfeasible to conventional electron spin resonance spectroscopy, which is widely used for coherent addressing of ensemble electron spins, due to its low initialization efficiency and readout sensitivity. Taking advantage of single spin detectability of single‐molecule spectroscopy, scanning tunneling microscopy, atomic force microscopy, and quantum metrology, several strategies have been developed to empower electron spin resonance spectroscopy with single qubit addressability. In this Emerging Topic, we introduce principles and technical implementation of strategies for coherent addressing of single molecular electron spin qubits, discuss their potential applicability in quantum technologies, and point out their challenges in terms of scalability, molecular design, and/or decoherence suppression. We discuss future directions to overcome these challenges and to improve single qubit addressing technologies, which will facilitate the advancement of molecular quantum information science.

Fast, Broad-Band Magnetic Resonance Spectroscopy with Diamond Widefield Relaxometry.

We present an alternative to conventional Electron Paramagnetic Resonance (EPR) spectroscopy equipment. Avoiding the use of bulky magnets and magnetron equipment, we use the photoluminescence of an ensemble of Nitrogen-Vacancy centers at the surface of a diamond. Monitoring their relaxation time (or T1), we detected their cross-relaxation with a compound of interest. In addition, the EPR spectra are encoded through a localized magnetic field gradient. While recording previous data took 12 min per data point with individual NV centers, we were able to reconstruct a full spectrum at once in 3 s, over a range from 3 to 11 G. In terms of sensitivity, only 0.5 μL of a 1 μM hexaaquacopper(II) ion solution was necessary.

In situ amplification of spin echoes within a kinetic inductance parametric amplifier

The use of superconducting microresonators together with quantum-limited Josephson parametric amplifiers has enhanced the sensitivity of pulsed electron spin resonance (ESR) measurements by more than four orders of magnitude. So far, the microwave resonators and amplifiers have been designed as separate components due to the incompatibility of Josephson junction-based devices with magnetic fields. This has produced complex spectrometers and raised technical barriers toward adoption of the technique. Here, we circumvent this issue by coupling an ensemble of spins directly to a weakly nonlinear and magnetic field-resilient superconducting microwave resonator. We perform pulsed ESR measurements with a 1-pL mode volume containing 6 × 107 spins and amplify the resulting signals within the device. When considering only those spins that contribute to the detected signals, we find a sensitivity of [Formula: see text] for a Hahn echo sequence at a temperature of 400 mK. In situ amplification is demonstrated at fields up to 254 mT, highlighting the technique's potential for application under conventional ESR operating conditions.

Symmetry of the Hyperfine and Quadrupole Interactions of Boron Vacancies in a Hexagonal Boron Nitride

The concept of optically addressable spin states of deep level defects in wide band gap materials is successfully applied for the development of quantum technologies. Recently discovered negatively charged boron vacancy defects (VB) in hexagonal boron nitride (hBN) potentially allow a transfer of this concept onto atomic thin layers due to the van der Waals nature of the defect host. Here, we experimentally explore all terms of the VB spin Hamiltonian reflecting interactions with the three nearest nitrogen atoms by means of conventional electron spin resonance and high frequency (94 GHz) electron-nuclear double resonance. We establish symmetry, anisotropy, and principal values of the corresponding hyperfine interaction (HFI) and nuclear quadrupole interaction (NQI). The HFI can be expressed in the axially symmetric form as Aperp = 45.5 MHz and Apar = 87 MHz, while the NQI is characterized by quadrupole coupling constant Cq = 1.96 MHz with slight rhombisity parameter n = (Pxx - Pyy)/Pzz = -0.070. Utilizing a conventional approach based on a linear combination of atomic orbitals and HFI values measured here, we reveal that almost all spin density (84 %) of the VB electron spin is localized on the three nearest nitrogen atoms. Our findings serve as valuable spectroscopic data and direct experimental demonstration of the VB spin localization in a single two dimensional BN layer.

Magnetometry of neurons using a superconducting qubit

Iron plays important physiological and pathological roles in the human body. However, microscopic analysis including redox status by a conventional electron spin resonance (ESR) spectrometer is difficult due to limited spatial resolution and sensitivity. Here we demonstrate magnetometry of cultured neurons on a polymeric film using a superconducting flux qubit that works as a sensitive magnetometer in a microscale area towards realizing ESR spectroscopy. By changing temperature (12.5–200 mK) and a magnetic field (2.5–12.5 mT), we observe a clear magnetization signal from the neurons that is well above the control magnetometry of the polymeric film itself. From ESR spectrum measured at 10 K, the magnetization signal is identified to originate from electron spins of iron ions in neurons. This technique to detect a bio-spin system can be extended to achieve ESR spectroscopy at the single-cell level, which will give the spectroscopic fingerprint of cells.

Conventional and high-field pulsed EPR experimental studies on Bazhenov oil formation under the influence of 50 Hz electromagnetic field

Heavy and extra-heavy oil are generating considerable interest in terms of replacing light oil role in the next few years. Nowadays, various enhanced oil recovery (EOR) methods are under development for an effective exploration and oil refining of unconventional oil sources. Electrical methods are among the most commonly discussed types of EOR techniques. Despite this interest, no one as far as we know has studied the effectiveness and mechanisms of electromagnetic (EM) heating influence on heavy oil conversion. It is common knowledge that heavy oils often contain stable paramagnetic centers, which potentially can serve as at least signaling species to follow the EOR upgrading degree. For the first time, to the best of our knowledge, pulsed and high-frequency (high-field, with 3.4 T detection magnetic field) electron paramagnetic resonance (EPR) techniques were exploited to investigate the EM heating influence on Bazhenov formation heavy oil by subjecting it to 50 Hz (0.75 T) electromagnetic field in laboratory conditions. The obtained samples were analyzed by a set of physico-chemical methods including SARA analysis (S: Saturates, A: Aromatics, R: Resins, A: Asphaltenes), gas chromatography–mass spectrometry (GCMS) in addition to pulsed and conventional (cw) EPR spectroscopy. SARA analysis has shown an increase in the content of asphaltenes from 1.2 ± 0.3 wt% in the initial oil to 1.4 ± 0.4, 1.4 ± 0.3, 1.3 ± 0.2, 1.3 ± 0.5 wt% in the samples obtained at 10, 20, 30 and 40 min respectively. Interestingly, this content has drastically dropped to 0.2 ± 0.05 and 0.3 ± 0.02 wt% in the samples obtained at 50 and 60 min of EM heating. Analogically for resins content change which has firstly increased from 1.5 ± 0.5 wt% in the initial oil to 1.9 ± 0.5, 2.6 ± 0.6, 3.0 ± 0.2, 3.0 ± 0.6 wt% in the samples obtained at 10, 20, 30 and 40 min respectively. Then this content has decreased to 0.5 ± 0.05 and 1.0 ± 0.04 wt% in the samples obtained at 50 and 60 min of EM heating. The content of saturated and aromatic compounds has been found to reach 99.3 ± 0.6 wt% in the sample obtained at 50 min comparing to 97.3 ± 1.1 wt% in the initial oil. Moreover, the GCMS data have showed a significant increase in the content of normal alkanes, which resulted from the processes of oil high molecular compounds fractions conversion as a consequence of alkyl substituents elimination. Our data points towards the idea that the investigated oil sample EPR signal intensity and their spectroscopic characteristics do not change with the EM heating either in the X- or W-band frequencies. g|| and g⊥ were found equal to 2.0024 and 2.0015 respectively at 3357 and 3358 mT for the initial sample and the obtained sample after 60 min of EM heating. Similar results (g||=2.0004 and g⊥=1.9991) were obtained for these samples at 3360 and 3362 mT. The findings of this study can help for better understanding of the mechanisms ruling the impact of electromagnetic heating on enhancing oil recovery.

Super-Resolution Airy Disk Microscopy of Individual Color Centers in Diamond

Super-resolution imaging techniques enable nanoscale microscopy in fields such as physics, biology, and chemistry. However, many super-resolution techniques require specialized optical components, such as a helical-phase mask. We present a novel technique, super-resolution Airy disk microscopy, that can be used in a standard confocal microscope without any specialized optics. We demonstrate this technique, in combination with ground state depletion, to image and control nitrogen-vacancy (NV) centers in bulk diamond below the diffraction limit. A greater than 14-fold improvement in resolution compared to the diffraction limit is achieved, corresponding to a spatial resolution of 16.9(8) nm for a 1.3 NA microscope with 589 nm light. We make use of our enhanced spatial resolution to control the spins states of individual NV centers separated from each other by less than the diffraction limit, including pairs sharing the same orientation that are indistinguishable with a conventional electron spin resonance measurement.

X-Band Parallel-Mode and Multifrequency Electron Paramagnetic Resonance Spectroscopy of S = 1/2 Bismuth Centers.

The recent successes in the isolation and characterization of several bismuth radicals inspire the development of new spectroscopic approaches for the in-depth analysis of their electronic structure. Electron paramagnetic resonance (EPR) spectroscopy is a powerful tool for the characterization of main group radicals. However, the large electron–nuclear hyperfine interactions of Bi (209Bi, I = 9/2) have presented difficult challenges to fully interpret the spectral properties for some of these radicals. Parallel-mode EPR (B1∥B0) is almost exclusively employed for the study of S > 1/2 systems but becomes feasible for S = 1/2 systems with large hyperfine couplings, offering a distinct EPR spectroscopic approach. Herein, we demonstrate the application of conventional X-band parallel-mode EPR for S = 1/2, I = 9/2 spin systems: Bi-doped crystalline silicon (Si:Bi) and the molecular Bi radicals [L(X)Ga]2Bi• (X = Cl or I) and [L(Cl)GaBi(MecAAC)]•+ (L = HC[MeCN(2,6-iPr2C6H3)]2). In combination with multifrequency perpendicular-mode EPR (X-, Q-, and W-band frequencies), we were able to fully refine both the anisotropic g- and A-tensors of these molecular radicals. The parallel-mode EPR experiments demonstrated and discussed here have the potential to enable the characterization of other S = 1/2 systems with large hyperfine couplings, which is often challenging by conventional perpendicular-mode EPR techniques. Considerations pertaining to the choice of microwave frequency are discussed for relevant spin-systems.

Electrically detected electron nuclear double resonance in amorphous hydrogenated boron thin films

We report on electrically detected electron nuclear double resonance (EDENDOR) observations via spin dependent trap assisted tunneling (SDTAT) in amorphous boron thin films at 250 K. We observe EDENDOR from both 10B and 11B nuclei, likely interacting with carbon impurities. In SDTAT, electron paramagnetic resonance (EPR) is detected through a change in the trap assisted tunneling current through the thin film. As in conventional electron nuclear double resonance (ENDOR) the ENDOR response is detected through a modest change in the EPR response. Since SDTAT detection sensitivity is about seven orders of magnitude greater than that of conventional EPR, it, in principle, can provide an enormous boost in ENDOR sensitivity. This enormous potential sensitivity improvement can be compromised by a coupling of the RF electromagnetic field driving the nuclear spin response and the electrical leads which are utilized to monitor the resonance induced changes in device current. We overcome this difficulty with the introduction of proportional-integral-derivative (PID) control of the RF circuitry which greatly suppresses fluctuations in the amplitude of the RF magnetic field at the thin film structure under investigation.

Accurate measurement of atomic magnetic moments by minimizing the tip magnetic field in STM-based electron paramagnetic resonance

Electron paramagnetic resonance (EPR) performed with a scanning tunneling microscope (STM) allows for probing the spin excitation of single atomic species with MHz energy resolution. One of the basic applications of conventional EPR is the precise determination of magnetic moments. However, in an STM, the local magnetic fields of the spin-polarized tip can introduce systematic errors in the measurement of the magnetic moments by EPR. We propose to solve this issue by finding tip-sample distances at which the EPR resonance shift caused by the magnetic field of the tip is minimized. To this end, we measure the dependence of the resonance field on the tip-sample distance at different radiofrequencies and identify specific distances for which the true magnetic moment is found. Additionally, we show that the tip's influence can be averaged out by using magnetically bistable tips, which provides a complementary method to accurately measure the magnetic moment of surface atoms using EPR STM.

Clustering of Stearic Acids in Model Phospholipid Membranes Revealed by Double Electron-Electron Resonance.

Free fatty acids play various important roles in biological membranes. Double electron-electron resonance spectroscopy (DEER, also known as PELDOR) of spin-labeled biomolecules is capable of studying magnetic dipole-dipole (d-d) interactions between spin labels at the nanoscale range of distances. Here, DEER is applied to study intermolecular d-d interactions between doxyl-spin-labeled stearic acids (DSA) in gel-phase phospholipid bilayers composed either of an equimolecular mixture of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine and 1,2-dioleoyl-sn-glycero-3-phosphocholine or of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine. DEER data obtained for different DSA concentrations showed that DSA molecules at their concentration in the bilayer χ larger than 0.5 mol % are assembled into lateral lipid-mediated clusters, with a characteristic intermolecular distance of 2 nm. Some evidences were obtained indicating that clusters may consist of "subclusters", alternatively appearing in two opposite leaflets. Conventional electron paramagnetic resonance (EPR) spectra for the gel-phase bilayers showed that for χ larger than 2 mol % the molecules in the clusters stick together, forming oligomers. Room-temperature EPR spectra for the liquid-crystalline phase were found to change noticeably for χ larger than 0.5 mol %, which may indicate the clustering in a liquid-crystalline phase similar to that observed by DEER in the gel phase.

High-Frequency and -Field Electron Paramagnetic Resonance Spectroscopic Analysis of Metal-Ligand Covalency in a 4f7 Valence Series (Eu2+, Gd3+, and Tb4+).

The recent isolation of molecular tetravalent lanthanide complexes has enabled renewed exploration of the effect of oxidation state on the single-ion properties of the lanthanide ions. Despite the isotropic nature of the 8S ground state in a tetravalent terbium complex, [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4], preliminary X-band electron paramagnetic resonance (EPR) measurements on tetravalent terbium complexes show rich spectra with broad resonances. The complexity of these spectra highlights the limits of conventional X-band EPR for even qualitative determination of zero-field splitting (ZFS) in these complexes. Therefore, we report the synthesis and characterization of a novel valence series of 4f7 molecular complexes spanning three oxidation states (Eu2+, Gd3+, and Tb4+) featuring a weak-field imidophosphorane ligand system, and employ high-frequency and -field electron paramagnetic resonance (HFEPR) to obtain quantitative values for ZFS across this valence series. The series was designed to minimize deviation in the first coordination sphere from the pseudotetrahedral geometry in order to directly interrogate the role of metal identity and charge on the complexes' electronic structures. These HFEPR studies are supported by crystallographic analysis and quantum-chemical calculations to assess the relative covalent interactions in each member of this valence series and the effect of the oxidation state on the splitting of the ground state and first excited state.

Deep Insights into Heavy Oil Upgrading Using Supercritical Water by a Comprehensive Analysis of GC, GC-MS, NMR, and SEM-EDX with the Aid of EPR as a Complementary Technical Analysis.

Upgrading of heavy oil in supercritical water (SCW) was analyzed by a comprehensive analysis of GC, GC–MS, NMR, and SEM–EDX with the aid of electron paramagnetic resonance (EPR) as a complementary technical analysis. The significant changes in the physical properties and chemical compositions reveal the effectiveness of heavy oil upgrading by SCW. Especially, changes of intensities of conventional EPR signals from free radicals (FRs) and paramagnetic vanadyl complexes (VO2+) with SCW treatment were noticed, and they were explained, respectively, to understand sulfur removal mechanism (by FR intensity and environment destruction) and metal removal mechanism (by VO2+ complexes’ transformation). For the first time, it was shown that electronic relaxation times extracted from the pulsed EPR measurements can serve as sensitive parameters of SCW treatment. The results confirm that EPR can be used as a complementary tool for analyzing heavy oil upgrading in SCW, even for the online monitoring of oilfield upgrading.

Wafer-Level near Zero Field Spin Dependent Charge Pumping: Effects of Nitrogen on 4H-SiC MOSFETs

In this work, we describe a new way to measure spin dependent charge capture events at MOSFET interfaces called near-zero-field spin dependent charge pumping (NZF SDCP) which yields similar information as conventional electron paramagnetic resonance. We find that NO anneals have a significant effect on the spectra obtained from 4H-SiC MOSFETs. We also likely resolve hyperfine interactions which are important for defect identification. Finally, we fully integrate a NZF SDCP measurement system into a wafer prober for high throughput applications.

Spectroscopic study of volcanic ashes

Volcanic ashes particles are subjected to substantial modification during explosive eruptions. The mineralogical and compositional changes have important consequences on the environment and human health. Nevertheless, the relationship between the speciation of iron (Fe) and the mineralogical composition and particle granulometry of the ashes, along with their interaction with water, are largely unknown. In particular, the Fe oxidation state and the possible formation of new Fe-bearing phases in presence of S, Cl, and F in the plume are key points to assess the impact of the ashes.Fragmental material ejected during volcanic activity (tephra) in 2013, was collected on the Mt. Etna (Italy) and investigated using a multi-technique approach that included conventional Electron Paramagnetic Resonance (EPR), high field EPR (HFEPR), EchoEPR, and Fe K-edge X-ray Absorption Spectroscopy (XAS). These element-selective techniques allowed obtaining a detailed information on the oxidation state and coordination environment of Fe, and of its speciation in the ash samples as a function of the granulometry. A complex mineralogical assemblage, consisting of variable amounts of nanometric crystalline Fe inclusions in a glass matrix, and of Fe-oxides and Fe-sulfur phases was revealed. A risk assessment of the ashes is attempted.

Electron spin resonance microfluidics with subnanoliter liquid samples

Microfluidics is a well-established technique to synthesize, process, and analyze small amounts of materials for chemical, biological, medical, and environmental applications. Typically, it involves the use of reagents with a volume smaller than ~ 1 micro-l—ideally even nano- or picoliters. When the sample of interest contains paramagnetic species, it can in principle be quantified and analyzed by electron spin resonance (ESR) spectroscopy. However, conventional ESR is typically carried out with a sample volume of ~ 1 ml, thereby making it incompatible with most microfluidics applications. Here we show that by using a new class of miniature surface resonators combined with photolithography to prepare microfluidic patterns, ESR can be applied to measure small liquid samples, down to picoliter volumes, without considerably sacrificing concentration sensitivity. Our experiments, carried out with resonators whose mode volumes range from ~1 to 3.6 nL, showed that with a sample volume of ~0.25 nL good signals could be obtained from solutions with spin concentrations of less than 0.1 μM. The advantage of using microfluidics ESR is evident in our work, not only because it facilitates the use of a very small sample volume, but also because it makes it possible to apply huge ( ~ 1000 T/m) and fast ( ~ 1 μs) pulsed magnetic field gradients to the sample. This is a key capability to measuring unique properties such as nanoscale real-space diffusion and quantum spin diffusion. All our experiments are performed at room temperature, making our technique compatible with future microfluidics applications that might employ a complete system of compact resonators, microfluidic chips, miniature magnets, and a compact ESR-on-a-chip spectrometer. This could result in a completely new approach to processing and measuring paramagnetic liquid samples for use in a variety of chemical, biological, medical, and environmental applications.

ESR, STESR, DFT, and MD Study of the Dynamical Structure of Cucurbituril[7]-Spin Probe Guest-Host Complexes.

We study the molecular dynamics and structures of the guest–host complexes of cucurbituril, CB[7], with spin probes through the conventional electron spin resonance (ESR), saturation transfer ESR (STESR), density functional theory (DFT), and molecular dynamics (MD) computations. Protonated TEMPOamine (I), a derivative of TEMPO having a positive charge and an octyl group on the quaternary nitrogen atom (II), and the neutral spin-labeled indole (III) are used as guests. To eliminate the overall complex rotation, the solutions of complexes in a solid CB[7] matrix were prepared. Resultantly, for all of the spin probes, the combined study of the conventional ESR and STESR spectra indicates the librational character of the rotational motion within the CB[7] cavity as opposed to the diffusional rotation over the whole solid angle. The kinetic accessibilities of the reporter NO groups to the paramagnetic complexes in aqueous solutions, determined by Heisenberg exchange broadening of the ESR spectra, together with the environment polarities from the hyperfine interaction values, as well as DFT computation results and MD simulations, were used to estimate the spin probe location relative to CB[7]. Utilizing the concept of the aqueous clusters surrounding the spin probes and CB[7] molecules and MD simulations has allowed the application of DFT to estimate the aqueous environment effects on the complexation energy and spatial structure of the guest–host complexes.

Purely Spectroscopic Determination of the Spin Hamiltonian Parameters in High-Spin Six-Coordinated Cobalt(II) Complexes with Large Zero-Field Splitting.

Accurate determination of the spin Hamiltonian parameters in transition-metal complexes with large zero-field splitting (ZFS) is an actual challenge in studying magnetic and spectroscopic properties of high-spin transition metal complexes. Recent critical papers have convincingly shown that previous determinations of these parameters, based only on the magnetic data, have low accuracy and reliability. A combination of X-band electron paramagnetic resonance (EPR) spectroscopy and SQUID magnetometry seems to be a more convincing and accurate approach. However, even in this case, the accuracy of the determination of the spin Hamiltonian parameters is strongly limited. In this work, we propose a purely spectroscopic approach, in which three complementary EPR spectroscopic techniques are used to unambiguously with high accuracy determine the spin Hamiltonian parameters for transition-metal complexes with S = 3/2. The applicability of this approach is demonstrated by analyzing the new quasi-octahedral high-spin Co(II) complex [Co(hfac)2(bpy)] (I). Along with the conventional X-band EPR spectroscopy, we also use such advanced techniques as multi-high-frequency EPR spectroscopy (MHF-EPR) and frequency-domain Fourier-transform THz-EPR (FD-FT THz-EPR). We demonstrate that the experimental data derived from the X-band and MHF-EPR EPR spectra allow determination of the g tensor (gx = 2.388, gy = 2.417, gz = 2.221) and the ZFS rhombicity parameter E/D = 0.158. The axial ZFS parameter D = 37.1 cm-1 is measured for I with the aid of FD-FT THZ-EPR spectroscopy, which is able to detect the high-energy EPR transition between the two Kramers doublets. CASSCF/NEVPT2 quantum-chemical calculations of magnetic parameters and magnetic direct current (dc) measurements are performed as well as testing options, and the results obtained in these ways are in good agreement with those derived using the proposed spectroscopic approach.

A portable EPR system for the absolute polarimetry of noble gases

A simple and portable electron paramagnetic resonance (EPR) system has been developed for the absolute polarimetry of noble gases polarized by spin-exchange optical pumping. By using modern digital technology together with software implementation of phase-sensitive detection and feedback control, the new system has become much more compact than the conventional EPR apparatus and can be easily transported anywhere. The main components of the new EPR system are a computer and a PC-based oscilloscope with a built-in function generator. The raw signal data is processed in real time by a computer, which offers great flexibility to the new system. By modifying the data-processing algorithm, it can be customized and applied to other scientific and engineering measurements that utilize phase-sensitive detection.

19F Paramagnetic Relaxation-Based NMR for Quaternary Structural Restraints of Ion Channels.

Quaternary distance restraints are essential to define the three-dimensional structures of protein assemblies. These distances often fall within a range of 10-18 Å, which challenges the high and low measurement limits of conventional nuclear magnetic resonance (NMR) and double electron-electron resonance electron spin resonance spectroscopies. Here, we report the use of 19F paramagnetic relaxation enhancement (PRE) NMR in combination with 19F/paramagnetic labeling to equivalent sites in different subunits of a protein complex in micelles to determine intersubunit distances. The feasibility of this strategy was evaluated on a pentameric ligand-gated ion channel, for which we found excellent agreement of the 19F PRE NMR results with previous structural information. The study suggests that 19F PRE NMR is a viable tool in extracting distance restraints to define quaternary structures.